JP2021513959A - Emm−37材料並びにその方法及び使用 - Google Patents
Emm−37材料並びにその方法及び使用 Download PDFInfo
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- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
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- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
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Abstract
Description
(m)X2O3:YO2 (式I)
(式中、0.01≦m≦0.25であり、Xは三価元素であり、Yは四価元素である)
を含む組成を有する多孔質結晶性EMM−37材料を提供する。EMM−37材料は、発明を実施するための形態の項及び実施例の項に記載されるような、式Iの三価及び四価の酸化物以外の成分を含むことができる。
(n)G:(v)X2O3:YO2 (式II)
(式中、0.01≦v≦0.25であり、0.03≦n≦0.25であり、Gは有機構造指向剤であり、Xは三価元素であり、Yは四価元素である)
を含む組成を有する製造されたままの形態の結晶性EMM−37材料が提供される。これらのEMM−37材料は、発明を実施するための形態の項及び実施例の項に記載されるような、式IIの三価及び四価の酸化物以外の成分を含むことができる。
(m)X2O3:YO2 (式I)
(式中、0.01≦m≦0.25であり、Xは三価元素であり、Yは四価元素である)
で表される組成を有することができる。Xは、B、Al、Fe、及びGa、又はそれらの混合物から選択することができる。例えば、Xは、Alを含むことができる、又はAlであってよい。Yは、Si、Ge、SnTi、及びZr、又はそれらの混合物から選択することができる。例えば、YはSiを含むことができるか、又はSiであってよい。式I中の酸素原子は、炭素原子(例えば、CH2の形態)で置換することができ、これは製造されたままのEMM−37の調製に使用される成分の供給源に由来することができる。式I中の酸素原子は、例えばSDAが除去された後に、窒素原子で置換することもできる。式Iは、一部又はすべてのSDAが除去されている典型的なEMM−37材料のフレームワークを表すことができるが、EMM−37材料の唯一の表現であることを意味するものではない。EMM−37材料は、SDA及び不純物を除去するための適切な処理の後にSDA及び/又は不純物を含む場合があり、これらは式I中には示されていない。さらに、式Iは、EMM−37材料中に存在しうるプロトン及び電荷補償イオンを含んでいない。
(n)G:(v)X2O3:YO2 (式II)
(式中、0.01≦v≦0.25であり、0.03≦n≦0.25であり、Gは有機構造指向剤であり、Xは三価元素であり、Yは四価元素である)
で表される組成を有することができる。Xは、B、Al、Fe、及びGa、又はそれらの混合物から選択することができる。例えば、XはAlを含むことができるか、又はAlであってよい。Yは、Si、Ge、Sn、Ti、及びZr、又はそれらの混合物から選択することができる。例えば、YはSiを含むことができるか、又はSiであってよい。式IIは、SDAを有する典型的な製造されたままのEMM−37材料のフレームワークを表すことができるが、このような材料の唯一の表現であることを意味するものではない。製造されたままのEMM−37材料は、式IIによって表されていない不純物を含む場合がある。さらに、式IIは、製造されたままのEMM−37材料中に存在しうるプロトン及び電荷補償イオンを含まない。式Iと同様に、式II中の酸素原子は、炭素原子(例えば、CH2の形態)で置換することができ、これは製造されたままのEMM−37の調製に使用される成分の供給源に由来することができる。
(i)水酸化物イオンの供給源と、四価元素Yの酸化物の供給源と、三価元素Xの供給源と、場合によりビスピロリジニウムジカチオンを含む構造指向剤(G)とを含む組成物を混合するステップと;
(ii)混合された組成物を加熱するステップと;
(iii)EMM−37材料の結晶を単離するステップと、
として記載することができる。
を有する化合物Hを含むことができる、又は化合物Hであってよい。
(i)化合物1:
(ii)化合物2を化合物3:
(iii)化合物3を化合物H:
(iv)場合により化合物Hを所望の立体異性体(例えば、RS異性体)に精製するステップと、
を含むことができる。
EMM−37材料(一部又はすべてのSDAが除去される場合)は、水素化成分と組み合わせることができる。水素化成分は、水素化−脱水素機能が行われる、モリブデン、タングステン、レニウム、ニッケル、コバルト、クロム、マンガン、又は白金若しくはパラジウムなどの貴金属から選択することができる。このような水素化成分は、以下の方法:共結晶化;IIIA族元素、例えばアルミニウムが構造中に存在する程度での組成物中への交換;その中への含浸、又はそれとの物理的混合の1つ以上によって組成物中に混入することができる。1つ以上の態様では、このような水素化成分は、EMM−37材料中に含浸させることができる。白金の場合、EMM−37材料に、白金金属含有イオンを含む溶液を含浸させることができる。含浸に適切な白金化合物は、クロロ白金酸、塩化第一白金、及び白金アミン錯体を含有する化合物から選択することができる。
1.6当量のメチルアミンを1当量の二無水物の1,1−ジメチル−3,3’−ビピロリジン−2,2’,5,5’−テトラオンと、マイクロ波中で15分で160℃まで上昇させ、160℃の温度を1時間維持することによって反応させた。溶媒として水を使用した。マイクロ波加熱の後、反応混合物を、約10mLのMeOH/1gのメソブタン−1,2,3,4−テトラカルボン酸無水物を含むメタノール溶液中に滴下した。5〜10分後、白色固体が溶液から沈殿した。この固体をフリット上で単離し、オーブン乾燥させた。得られた白色結晶性固体(56%の収率)は、1H NMRによって測定すると純粋な化合物2であった。
3000mlの3口丸底フラスコにオーバーヘッド撹拌機及び還流冷却器を取り付けた。次にこのフラスコに1500mLのテトラヒドロフランを加えた。次に16.89gのペレット形態の水素化アルミニウムリチウム(LAH)を加え、得られた懸濁液を激しく終夜撹拌した。次にフラスコの周囲に氷浴を配置した。次に、31.56gの1,1’−ジメチル−[3,3’−ビピロリジン]−2,2’,5,5’−テトラオン(化合物2)を約2時間にわたって5gずつ撹拌混合物に徐々に加えた。次に混合物を終夜撹拌した。翌朝、フラスコの下に加熱マントルを配置し、次に懸濁液を2時間還流させた。次にフラスコを氷浴中で冷却し、混合物に約400mlのジエチルエーテルを加えた。次にこの時点で、激しい撹拌下で200mLの45%NaOH溶液を滴下した。灰色固体が白色になった後、固体を濾過によって除去し、分液漏斗を用いてTHF/エーテル層を単離した。次にこの溶液を無水硫酸マグネシウムで乾燥させ、次に濾過によって固体を除去した。次に、回転蒸発によってジアミン(化合物3)を回収して、63%の収率の生成物を得た。この手順を繰り返して、より多い量のジアミン(化合物3)を製造した。1H NMR及び13C NMRによって、生成物が2つの異性体の約60/40の混合物であることが示された。
51.92gのジアミン(化合物3)を300mLのメタノールに加えた。次に、激しく撹拌しながらこの混合物に132gのヨードメタンを滴下した。翌日、固体沈殿物を濾過によって単離した。1H及び13C NMRによって、生成物が約95%異性体Aであることが示された。溶媒の回転蒸発によって、残りの生成物を単離した。回転蒸発で得られた固体残留物をアセトンで洗浄し、次に終夜乾燥させた。1H及び13C NMRによって、溶媒から回収した生成物が約92%異性体Bであることが示された。最初に回収した固体を、最小限の脱イオン水を加えた熱メタノールから2回再結晶させることによってさらに精製した。再結晶によって、大きな結晶が得られ、これらを単結晶X線回折の構造解に使用した。47gの異性体A及び33gの異性体Bが得られた。単結晶構造解によって、異性体AがRSジアステレオマーであることが示された。異性体BはRR及びSSの鏡像異性体であり、これらの鏡像異性体は互いに分離しなかった。
異性体Aを水中に溶解させ、それを700mLのDowex LC NG水酸化物に加えることによって、その水酸化物形態に変換した。翌日、樹脂を濾過によって取り出し、脱イオン水で洗浄して、樹脂から生成物を取り出した。次に水性画分を1つにまとめ、減圧下で60℃で濃縮した。0.1NのHClの標準溶液を用いた滴定によって測定すると、この水溶液の水酸化物濃度は1.86mmolOH−/gであった。
以下の実験1〜11の合成において、アルミニウム源としてメタカオリンを使用した。実施例1で得た化合物Hをメタカオリン、NaOH、脱イオン水、及びLUDOX(登録商標)AS−40と混合した。次にTeflonライナーにキャップを取り付け、鋼製Parrオートクレーブの内部に封入した。次にこのオートクレーブを、160℃に維持した対流オーブン中、転動条件下で7〜14日間加熱した。生成物を遠心分離によって単離し、脱イオン水中に再懸濁させ、次にさらに遠心分離を行った。このプロセスを3回繰り返し、粉末XRD用の試料を収集した。
23mLのTeflonライナー中で、2.65gの化合物Hの水酸化物の溶液(異性体A)([OH−]=1.86mmol/g)を、0.93gのメタカオリン、0.40gの50%NaOH、5.67gの脱イオン水、及び2.24gのLUDOX(登録商標)AS−40と混合し、この混合物に0.053gのEMM−37の種晶を加えた。次に上記Teflonライナーにキャップを取り付け、23mLの鋼製Parrオートクレーブの内部に封入した。次にオートクレーブを、160℃に維持した対流オーブン中、転動条件(約40rpm)下で7日間加熱した。次に生成物を濾過によって回収して、約250mLの脱イオン水で洗浄した。粉末XRD(図1)によって、生成物が製造されたままの形態の純粋なEMM−37であることが示された。この粉末パターンは、a=8.82、b=9.63、c=10.65Å、及びα=104.4、β=99.9、γ=99.5°の三斜晶系セルに帰属することができた。表4は、製造されたままのゼオライトのピーク及び強度の一覧を示している。空気中のTGAによって、225〜700℃の間で約21.5%の質量減が示された。
反応物の量を2.7倍にしたことを除けば、実施例3のような実験を繰り返した。粉末XRDによって、生成物が純粋なEMM−37であることが示された。試料をマッフル炉中、窒素下で温度を2℃/分で400℃まで上昇させ、次に空気中2℃/分で515、540、又は600℃まで温度を上昇させることによって焼成した。温度を515、540、又は600℃で2時間維持した後、それぞれの試料を周囲温度まで冷却した。
Claims (21)
- 0.10〜0.28cc/gの微細孔容積を有する、請求項1又は2に記載の材料。
- 式I:
(m)X2O3:YO2 (式I)
(式中、0.01≦m≦0.25であり、Xは三価元素であり、Yは四価元素である)
を含む組成を有する、請求項1〜4のいずれか一項に記載の材料。 - YのXに対する比が5〜25である、請求項5に記載の材料。
- aパラメータが8.8±0.3Åであり、bパラメータが9.6±0.3Åであり、cパラメータが10.7±0.3Åであり、αが104±6°であり、βが100±6°であり、γが100±6°である三斜晶系単位セルを有する、請求項7に記載の材料。
- 式II:
(n)G:(v)X2O3:YO2 (式II)
(式中、0.01≦v≦0.25であり、0.03≦n≦0.25であり、Gは有機構造指向剤であり、Xは三価元素であり、Yは四価元素である)
を含む組成を有する、請求項7〜9のいずれか一項に記載の材料。 - YのXに対する比が5〜25である、請求項10に記載の材料。
- GのYに対する比が0.05〜0.15である、請求項10に記載の材料。
- 水酸化物イオンの供給源と、四価元素Yの酸化物の供給源と、三価元素Xの供給源と、ビスピロリジニウムジカチオンを含む構造指向剤(G)とを含む組成物を混合するステップを含む、請求項7〜12のいずれか一項に記載の結晶性材料の調製方法。
- 前記結晶性材料から一部又はすべての前記構造指向剤を除去するステップをさらに含む、請求項13に記載の方法。
- 化合物HがRS異性体を含むか、又はRS異性体である、請求項15に記載の構造指向剤。
- 化合物3の前記変換の反応生成物から化合物HのRS異性体を単離するステップをさらに含む、請求項17に記載の方法。
- 有機化合物を請求項1〜6のいずれか一項に記載の結晶性材料に接触させるステップを含む、前記有機化合物を変換生成物に変換する方法。
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